New dyestuffs



United States Patent 3,088,949 NEW DYESTUFFS Eduard Moser, Bottmingen,and Jacob Koch, Basel, Switzerland, assignors to Ciba Limited, Basel,Switzerland, :1 Swiss company No Drawing. Filed Dec. 6, 1960, Ser. No.73,968 Claims priority, application Switzerland Dec. 8, 1959 1 Claim.(Cl. 260-481) Patented May 7, 1963 naphthoquinone,2:3-dibromo-naphthoquinone or 2:3: 6 'I-tetrabromo-naphthoquinone.

There are advantageously used the chlorides of the 2:3-phthaloyl-pyrrocoline carboxylic acids. The latter can be obtained bytreating the carboxylic acids in known manner with an acid-chlorinatingagent, for example, phosphorus trichloride, phosphorus pentachloride orhos phorus oxychloride, and more especially thionylchloride.

The treatment with the aforesaid acid-halogenating This inventionprovides dyestuffs of the general formula agents is advantageouslycarried out in an inert organic (1) on) (Rap in which R R R and R eachrepresent a hydrogen atom or a substituent not imparting solubility inwater, or R and R or R and R when in ortho-position relatively to eachother may together with the vicinal carbon atoms to which they are boundform a ring, m, n, p and q each represent the whole number I or 2, and Brepresents an aromatic radical which consists of at least twocarbocyclic rings condensed together and is free from groups impartingsolubility in water.

The invention also provides a process for the manufacture of thedyestufis of the above Formula 1, wherein two molecular proportions ofan halide of 2:3-phthaloylpyrroooline-l-carboxylic acide of the generalformula (the numbering of the pyrrocoline ring being that of PattersonsRing Index}, in which R R R R 111, n, p and q have the meanings givenabove, are condensed with one molecular proportion of an aromaticdiamine which contains at least two carbocyclic rings condensed with oneanother and is free from groups imparting solubility in water forexample sulfonic and carboxylic acid groups.

In the phthaloyl-pyrrocoline carboxylic acids of the Formula 2 R and Radvantageously represent hydrogen atoms or simple substituents, such ashalogen atoms or lower alkyl groups, or R and R when bound to vicinalcarbon atoms of the pyridine ring, may form together with those carbonatoms an alicyclic, heterocyclic, or aromatic ring. R, and Radvantageously represent hydrogen atoms or halogen atoms, for example,chlorine or bromine atoms.

The 2:3-phthaloyl-pyrrocoline carboxylic acids of the Formula 2 can beobtained, for example, by the process of U.S. Patent No. 2,877,230,patented March 10, 1959 by Robert S. Long et 211. by condensing a2:3-dihalogennaphthoquinone with an acetoacetic acid alkyl ester andpyridine or a substitution product thereof, for example,

or 'y-picoline, and hydrolising to the carboxylic acid the alkyl esterso obtained. As naphthoquinones there may be mentioned owing to the easewith which it can be obtained, more especially,2:3-dichloro-naphthoquinone. Alternatively, there may be used 2:3 :5 or2:3 :G-trichlorosolvent, such as dimethyl formamide, a chlorobenzene,for example, monoor di-chlorobenzene, toluene, xylene, or nitrobenzene.When the last mentioned solvent is used the reaction can be acceleratedby the addition of a small proportion of dimethyl formamide.

For making the carboxylic acid halides it is of ad vantage first to drythe carboxylic acid which has been prepared in an aqueous medium or tofree it from water azeotropically by boiling in an organic solvent. Thisazeotropic drying may, if desired, be carried out immediately before thetreatment with an acid-halogenating agent.

As aromatic diamines which contain at least two carbocyclic ringscondensed together there may be mentioned diamino naphthalenes, forexample, 1:3-, 1:4-, 1:5-, 126-, 1:8-, 2:6- or 2:7-diaminonaphthalene,or diaminochrysenes, for example, 2:8-diaminochrysene,2:7-diaminofluorene, 2:7-diamino-fluorenone, 1:4- 1:5-, 2:6-,2:7-diarnino-anthroquinone, l :5 -dichloro-2 6-diamino-anthraquinone, 4:8-dichloro-1 :S-diarnino-anthroquinone, 2 6-dibrorno-l:5-diarnino-anthroquinone, 3 :7-dibrorno-2 6-diamino-anthraquinone, l z5dibromo-2 ti-diamino-anthraquinone, 3:6dibromo-2:7-diamino-anthraquinone, 1:5- dinitro-flzfi-diaminoanthraquinone, l:5diamino-4:8-dihydroxy-anthaquinone, l:5-diamino-4-hydroxy-anthraquinone, 1:8-diarnino 3 :6dichlor-anthraquinone, 1:8-diamino-4 5-dihydroxy-anthraquinone,Srnethyl-l :4-diamino-anthraquinone, 2 S-dichloro-l :4-diamino-anthraquinone, 2:4:618-tetrachloro-1 :S-diaminoanthraquinone,214:6:B-tetrabromo-l:S-diaminoanthraquinone, 1:3 :5 :7- tetrachloro 1:5diamino anthraquinone, 1:3 :5z7-tetrabromo-Z G-diamino-anthraquinone, l:4 5 8tetraarninoanthraquinone, l:2:5:6-tetraaminoanthraquinone,2:6-dimethyl-anthraquinone, 2:7-dimethyl-anthraquinone, 2:5 and/or2:7-diaminophenanthraquinone, diaminoanthraquinone,3:6-diaminophenanthrenquinone, 5: IO-diaminopyrene-3z8-quinone,diaminoacedianthrone (obtainable, for example, by nitrating and reducingacedianthrone), perylee-3 :4 9: lO-tetracarboxylicacid-di-(3-aminophenylimide), perylene 3:4:9zl0 tetracarboxylicacid-di-(4- aminophenylimide), perylene 3 :4:9: 10 tetracarboxylic aciddi-para-amino-diphenylimide and 6:7-dimethoxyperylene-3z4z9:l0tetracarboxylic. acid-di-[aniinophenylimide).

The condensation of the phthaloyhpyrrocoline carboxylic acid halideswith the diamines is advantageously carried out in an anhydrous medium.Under these conditions the condensation generally takes placesurprisingly easily at temperatures within the boiling ranges ofordinary organic solvents, toluene, monochlorobenzene, dichlorobenzene,trichlorobenzene, nitrobenzene and the like. For accelerating thereaction there may be used an acid-binding agent, such as anhydroussodium-acetate, pyridine or anhydrous ammonia. The dyestuffs aregenerally obtained in very good yield and in a pure state. For makingespecially pure dyestuffs it may be of ad vantage first to separate theacid chlorides of the carboxylic acids and, if desired, to recrystallisethem. In most cases, especially when thionyl chloride is used asacidhalogenating agent, it is possible without harm, and in some caseseven with an improved result, to dispense with isolation of the acidchloride and to proceed with the condensation immediately after the acidchlorides have been made.

The dyestuffs of this invention are useful for dyeing a very widevariety of materials, for example as vat dyestuffs for dyeing cellulosefibers or animal fibers, such as wool or silk, or synthetic fibers suchas fibers of polyamides or polyesters. The dyestuffs of the inventioncan be sulfonated and used in the sulfonated condition for dyeing theaforesaid fibers. They are also useful as pigments for all uses ofpigments, for example, in the so-called pigment printing method, that isto say, a method of printing in which a pigment is fixed by means of asuitable adhesive, such as casein, a hardenable synthetic resin,especially a ureaor melamine-formaldehyde condensation product, or asolution or emulsion of polyvinyl chloride or polyvinyl acetate or otheremulsion, for example, an oil-in-water or water-in-oil emulsion, on asubstratum, especially on a textile fiber, but if desired, on anotherfiat structure such as paper, for example, wall paper, or a fabric ofglass fibers. The pigments are also useful for other purposes, forexample, in a finely dispersed form for coloring artificial silk ofviscose or a cellulose ether or ester or of a polyamide or polyurethanein the spinning mass, and also for making colored lacquers orlacquer-formers, solutions or products of acetyl-cellulose,nitro-cellulose, natural substances of high molecular Weight, such asrubber or casein, or synthetic resins, such as polymerization resins,for example, polyvinyl chloride, polyethylene, polypropylene,polystyrene, or condensation resins, for example, aminoplasts,phenoplasts and also silicone or silicone resins. They can also be usedwith advantage for making color pencils, cosmetic preparations orlaminated plates.

By virtue of their chemical inertness and good resistance to heat thepigments of this invention can be dispersed in the normal manner incompositions or products of the above kind, and this can be achievedwith advantage at a stage in the manufacture of such compositions orproducts before they have reached their final form. The pigments can beconverted by the known conditioning methods into a finely divided form.

The operations necessary for shaping, such as spinning, pressing,hardening, casting, sticking or the like can then be carried out in thepresence of the pigments.

The pigments of this invention are distinguished by their excellentfastness to light and migration.

The following examples illustrate the invention, the parts andpercentages being by weight.

Example 1 309 parts of 2:3-phthaloylpyrrocoline-l-carboxylic acidchloride (prepared according to US. Patent No. 2,877,230, patented March10, 1959 by Robert S. Long et al. by heating 2:3-dichloronaphthoquinone,acetoacetic acid ester and pyridine, hydrolysing the resulting2:3-phthaloylpyrrocoline-l-carboxylic acid ethyl ester to form thecarboxylic acid and reacting the latter with thionyl chloride) aresuspended at 115 C. in 700 parts of anhydrous ortho-dichlorobenzene;after about 20 minutes a clear solution is obtained into which, in thecourse of about 5 minutes, a solution heated at 120 C. of 7.9 parts of1:5diaminonaphthalene in 100 parts of anhydrous ortho-dichlorobenzeneand 2.5 parts of anhydrous pyridine is added. The mixture is heated to140 to 145 C. and maintained at this temperature for 10 hours, thenallowed to cool to 100 C., filtered, and the resulting pigment is washedwith ortho-dichlorobenzene heated at 100 C. until the solvent runs offpractically colorless. The product is washed with a small amount of coldmethanol and thereupon with hot water. The violet pigment is dried invacuo at to C. When used for coloring polyvinyl chloride foils, ityields a violet coloration which has good fastness to migration.

When 1:5-diaminonaphthalene is replaced by an equivalent amount of2:8-diaminochrysene, the resulting pigment colors polyvinyl chloridefoils brown shades.

By using diaminofiuoranthrene of the formula a brown shade is obtained.

With 3:8-diaminopyrene a violettish brown is obtained and with1:S-diamino-Z:6-dimethoxynaphthalene a neutral brown shade.

Example 2 34.4 parts of 4'- or 5'-chlorophthaloylpyrrocoline-carboxylicacid chloride, dissolved in 750 parts of anhydrous ortho-dichlorobenzeneat C., are treated at C. with a solution of 7.9 parts of1:5-diaminonaphthalene in 100 parts of anhydrous ortho-dichlorobenzeneand 2.5 parts of anhydrous pyridine. The resulting pigment colorspolyvinyl chloride foils violet shades having good fastness tomigration.

When 1:5-diaminonaphthalene is replaced by an equivalent amount ofdiaminofiuoranthene, a brown shade is obtained and with3:8-diaminopyrene a yellowish brown.

Example 3 2.4 parts of 1:5-diaminoanthraquinone and 6.2 parts of2:3-phthaloylpyrrocolinecarboxylic acid chloride are added to 100 partsof nitrobenzene. The mixture is heated with stirring to to 200 C. andmaintained for about one hour at this temperature. After cooling, thecondensation product is suctioned off, washed with alcohol and dried, toyield 7.5 parts of an orange dyestuff which dyes cotton from a reddishbrown vat very pure orange tints having good properties of fastness.

When 1:5-dian1inoanthraquinone is replaced by other vattable diamines,similar dyestuffs are obtained whose vat colors and shades of dyeings oncotton are shown in the following table:

Color of Shade of No. Vattahle diamino compound vat dyeing on cotton 1.1:4-tlia1ninoanthraqulnone reddish brown brown. orange. 2.1:6diamin0anthraquinone do orange, 3"... 1:8-dlaminoanthraquinone ..d0..yellow Orange. 4- 2 ti-diaminoanthraquinone brown red orange. 5.2:7diarninoanthraquinone... .do Do, 6t:8-rliamino-3:6-dtchloroanthraquinone. reddish yellow brown. Orange. 7.123:5 7-tetrachloro-2 fi-dimninoanthra .-do orange.

quinonc. 8. 1:5-tliamino-4:841thydroxy-anthraquinone do violet. 9-. 4:4diamino-l:1'-dinnthraquin0ylimidebrown currant.

r rbazole. orange. 10. 5:5- lia1nlno-1z1'-dianthraquiuoylirnide docoppery earbazole. red. 11. diamino-acedianthrone navy... brown.

When instead of the chloride of 2:3-phthaloylpyrrocoline-carboxylic acidthe chloride of the 4'-chloro derivative of said acid is used, dyestuffshaving similar properties are obtained.

Example 4 5.7 parts of finely distributedperylene-3:4:9:l(l-tctracarboxylic acid-NzN di meta aminophenylimide areheated with stirring to 180 C. in 210 parts of nitrodisintegrated in aHollander with 10,000 parts of water. benzene. 6.2 parts of2:3-phthaioyl-pyrrocolinc-carbox- 30 parts of the pigment obtained asdescribed in Exylic acid chloride are added and the mixture is heatedfor ample 1 are incorporated in the pulp thus prepared. another 3 hoursat 190 to 200 C. After cooling, the To fix the pigment, 16 parts ofaluminum sulfate are resulting condensation product is suctioned ott,washed 5 added. The colored fancy paper is impregnated in an withalcohol and dried, to yield 9 parts of a red dyestuff aqueous solutionof 50% strength of dimethylol which dyes cotton from a ruby vat strongruby tints melamine, squeezed and dried at 100 C. having good propertiesof fastness. (d) Depending on the desired quality of the laminate, the

When the condensation product of perylenetetracarfancy paper isprotected with tissue paper of bleached boxylic acid dianhydride with1:3-diaminobenzene is 10 special cellulose, weighing 40 grams per squaremeter. replaced by its condensation product with l:4diarnino- The tissuepaper is likewise impregnated with an aquebenzene or benzidine,dyestuffs having similar properties ous solution of 50% strength ofdimethylolmelamine, are obtained. squeezed and dried at 100 C.

Examp 1e 5 Equal pieces of the material prepared in this manner,

65 parts of polyvinyl chloride, 35 parts of dioctylmeasuring for example2.75 x 1.25 meters, are placed one phthalate and 0.2 part of the pigmentobtained as de on top of the other in the following order: 3 to 5 sheetsscribed in paragraph 1 of Example 1 are stirred together of paper (a), 1sheet of paper (b), 1 sheet of paper (c) and then rolled to and frobetween the two rollers of a a d, i th giv n ca e, 1 h t of paper (d),and the sandcalender for 7 minutes at 145 C. The resulting red foil wichis then compressed between mirror-chromed platens has good fastness tolight and migration. When, in addifor 12 minutes at 140 to 150 C. undera pressure of 100 tion to the amount of color pigment specified above,there kg. per sq. cm., cooled to 30 C., and the laminate thus are used 5parts of titanium dioxide, a violet pastel shade produced is removedfrom the press. 011 one side it is of is obtained. a violet color whichhas good resistance to light.

Example 6 Example 8 part of the diiesmfi obtained Example 1 are 1 partof the dyestulf obtained as described in Example ground for hours.m arod parts of an 3 is vatted in 100 parts of water containing 4 parts byalkydmalamme stovmg lacquer contammg 50% of volume of sodium hydroxidesolution of strength solids, and 4.75 parts of titanium dioxide. Theresulting with 2 parts of Sodium hydrosulfite at 0 C The Sum lacquer 1Sbrushed in a thin layer on an alumrnum foil 30 ing stock vat is dd d toa l tion of 4 parts by volume and stoved for one hour at 120 C. Theresulting violet of Sodium hydroxide solution of 39% Strength and 2parts lacquer coat has good fastness to light. of sodium hydrosulfite in2000 parts of water. 100 parts Example 7 of cotton are dyed in theresulting dyebath for one hour at 40 to 50 C. in the presence of 10parts of sodium. chloride. The cotton is then squeezed, oxidized in air,rinsed, acidified, once more rinsed and then soaped at the For themanufacture of a laminate the following component plies are prepared:

(a) Thick paper of unbleached sulfate cellulose (soboil. The resultingorange dyeing has good fastness called Kraft paper) is impregnated withan aqueous properties. phcnolformaldehyde resin solution, squeezed anddried. What is claimed is:

(b) Paper of pure, chemically bleached ccllulose,contain- The dyestutfof the formula 0 0 ll N N l CCONH NHOC-C oo -co ing zinc sulfide ortitanium dioxide as filler, is impreg- References Cited in the file ofthis patent nated with an aqueous solution of stren th of dimethylolmelamine, squeezed and dried at C. UNITE]? STATES PATENTS (c) 400 partsof a fancy paper of bleached cellulose, 2,772,274 Schmidt-Nickels etNOV-27,1956

containing zinc sulfide or titanium dioxide as filler, are 2,773,873Randall et a1 Dec. 11, 1956

